U.S. patent application number 15/429471 was filed with the patent office on 2017-08-24 for modifier for curable compositions comprising benzyl alcohol alkoxylates.
The applicant listed for this patent is Evonik Degussa GmbH. Invention is credited to Jurgen Kirchner, Matthias Lobert, Ellen Reuter, Katrin Roland.
Application Number | 20170240692 15/429471 |
Document ID | / |
Family ID | 55450995 |
Filed Date | 2017-08-24 |
United States Patent
Application |
20170240692 |
Kind Code |
A1 |
Roland; Katrin ; et
al. |
August 24, 2017 |
MODIFIER FOR CURABLE COMPOSITIONS COMPRISING BENZYL ALCOHOL
ALKOXYLATES
Abstract
The present invention relates to a modifier comprising benzyl
alcohol-based alkoxylates for curable compositions comprising at
least one epoxy resin and a hardener, which are obtained by
reacting benzyl alcohol with alkylene oxides, the benzyl
alcohol-based alkoxylates having at least one ethoxy fragment.
Inventors: |
Roland; Katrin; (Essen,
DE) ; Lobert; Matthias; (Essen, DE) ;
Kirchner; Jurgen; (Essen, DE) ; Reuter; Ellen;
(Bochum, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Evonik Degussa GmbH |
Essen |
|
DE |
|
|
Family ID: |
55450995 |
Appl. No.: |
15/429471 |
Filed: |
February 10, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 59/1438 20130101;
C09D 163/00 20130101; C08G 59/50 20130101; C08G 59/685 20130101;
C08G 59/68 20130101 |
International
Class: |
C08G 59/68 20060101
C08G059/68; C09D 163/00 20060101 C09D163/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 19, 2016 |
EP |
16156475.2 |
Claims
1. A modifier comprising benzyl alcohol-based alkoxylates for
curable compositions comprising one epoxy resin and one hardener,
wherein the benzyl alcohol-based alkoxylate is obtained by reacting
benzyl alcohol with alkylene oxides, wherein the benzyl
alcohol-based alkoxylate having at least one ethoxy fragment.
2. The modifier according to claim 1, wherein the benzyl
alcohol-based alkoxylate comprises benzyl alcohol-based ethoxylates
or benzyl alcohol-based mixed alkoxylates of the formula (I)
##STR00002## where a=alkoxy fragment (a)=1 to 10, b=alkoxy fragment
(b)=0 to 10, c=alkoxy fragment (c)=0 to 10, R1, R2=independently
hydrogen, an alkyl group having 2 to 20 carbon atoms, an aryl or
alkaryl group, with the proviso that R1 is not H when R2 is methyl,
and that the two R1 and R2 radicals must not both be H at the same
time, R3=independently a hydrogen radical, an acetyl, phosphoric
ester or alkyl group which has 1 to 20 carbon atoms and may also
have further substitution.
3. The modifier according to claim 2, wherein the alkylene oxides
are selected from the group consisting of-ethylene oxide (EO),
propylene oxide (PO), 1,2-epoxy-2-methylpropane (isobutylene
oxide), epichlorohydrin, 2,3-epoxy-1-propanol, 1,2-epoxybutane
(butylene oxide, BO), 2,3-epoxybutane,
2,3-dimethyl-2,3-epoxybutane, 1,2-epoxypentane,
1,2-epoxy-3-methylpentane, 1,2-epoxyhexane, 1,2-epoxycyclohexane,
1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane,
1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, styrene
oxide (SO), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane,
vinylcyclohexene oxide, (2,3-epoxypropyl)benzene, vinyloxirane,
3-phenoxy-1,2-epoxypropane, 2,3-epoxy methyl ether, 2,3-epoxy ethyl
ether, 2,3-epoxy isopropyl ether, 3,4-epoxybutyl stearate,
4,5-epoxypentyl acetate, 2,3-epoxypropane methacrylate,
2,3-epoxypropane acrylate, glycidyl butyrate, methyl glycidate,
ethyl 2,3-epoxybutanoate, 4-(trimethylsilyl)butane 1,2-epoxide,
4-(triethylsilyl)butane 1,2-epoxide,
3-(perfluoromethyl)-1,2-epoxypropane,
3-(perfluoroethyl)-1,2-epoxypropane,
3-(perfluorobutyl)-1,2-epoxypropane,
3-(perfluorohexyl)-1,2-epoxypropane, 4-(2,3-epoxypropyl)morpholine,
1-(oxiran-2-ylmethyl)pyrrolidin-2-one.
4. The modifier according to claim 3, wherein the alkylene oxides
are used individually or in any desired mixtures for alkoxylation
of the benzyl alcohol.
5. The modifier according to claim 4, wherein the benzyl
alcohol-based mixed alkoxylate is prepared by reacting ethylene
oxide (EO) and propylene oxide (PO) in a molar ratio of 1:10 to
10:0.
6. The modifier according to claim 5, wherein the alkoxy fragments
(a) and (b) may be added onto the benzyl alcohol in statistical or
random distribution.
7. The modifier according to claim 2, wherein the degree of
alkoxylation is 3 to 10.
8. The modifier according to claim 2, wherein the benzyl
alcohol-based alkoxylate has a terminal hydroxyl group.
9. The modifier according to claim 1, wherein the terminal hydroxyl
group of the benzyl alcohol-based alkoxylate is acetylated,
methylated or phosphorylated.
10. The modifier according to claim 2, wherein the polydispersity
(Mw/Mn) of the benzyl alcohol-based mixed alkoxylates of formula
(I) is <2.5, determined by means of GPC.
11. A method of making a benzyl alcohol-based alkoxylates
comprising the steps of mixing at least one epoxy fragment as
modifiers for curable compositions comprising at least one epoxy
resin, and at least one hardener, and further auxiliary
components.
12. The method according to claim 11 of formula (I) ##STR00003##
where a=alkoxy fragment (a)=1 to 10, b=alkoxy fragment (b)=0 to 10,
c=alkoxy fragment (c)=0 to 10, R1, R2=independently hydrogen, an
alkyl group having 2 to 20 carbon atoms, an aryl or alkaryl group,
with the proviso that R1 is not H when R2 is methyl, and that the
two R1 and R2 radicals must not both be H at the same time,
R3=independently a hydrogen radical, an acetyl, phosphoric ester or
alkyl group which has 1 to 20 carbon atoms and may also have
further substitution.
13. A curable composition comprising (1) at least one epoxy resin,
(2) at least one hardener, (3) at least one modifier according to
claim 1, and (4) further auxiliary components.
14. The curable composition according to claim 13, wherein
bisphenol A diglycidyl ether-based epoxy resins or bisphenol F
diglycidyl ether-based epoxy resins are used.
15. The curable composition according to claim 14, wherein the at
least one hardener (2) is an aminic hardener selected from the
group consisting of aliphatic, cycloaliphatic, araliphatic or
aromatic amines or polyamines.
16. The curable composition according to claim 15, wherein the at
least one hardener (2) is an acidic hardener selected from the
group consisting of acids and acid anhydrides.
17. A method of making floor coatings, paints, polymer concrete,
repair systems, anchoring compounds, adhesives, potting compounds
and impregnations, fiber composite materials comprising the step of
mixing the curable composition of claim 13 with other ingredients
to prepare floor coatings, paints, polymer concrete, repair
systems, anchoring compounds, adhesives, potting compounds and
impregnations, fiber composite materials.
18. The method of claim 11, wherein the at least one hardener is an
aminic hardener selected from the group consisting of aliphatic,
cycloaliphatic, araliphatic or aromatic amines or polyamines.
19. The method of claim 11, wherein the at least one hardener is an
is an acidic hardener selected from the group consisting of acids
and acid anhydrides.
20. The modifier according to claim 1, wherein the benzyl
alcohol-based alkoxylate comprises benzyl alcohol-based ethoxylates
or benzyl alcohol-based mixed alkoxylates of the formula (I)
##STR00004## where a=alkoxy fragment (a)=2 to 7, b=alkoxy fragment
(b)=1 to 7, c=alkoxy fragment (c)=0 to 6, R1, R2=independently
hydrogen, ethyl, octyl, decyl or phenyl group, with the proviso
that R1 is not H when R2 is methyl, and that the two R1 and R2
radicals must not both be H at the same time, R3=independently a
hydrogen radical.
Description
[0001] The present invention relates to a modifier comprising
benzyl alcohol-based alkoxylates for curable compositions
comprising at least one epoxy resin and a hardener, to the use
thereof and to curable compositions comprising said modifier.
[0002] Epoxy resins are known raw materials for the production of
high-quality casting resins and coating materials. The reaction of
these resins with a number of hardeners, especially with aminic
hardeners, leads to crosslinked polymers that can be thermoset
polymers and can be used in the fields of, for example, civil
engineering, particularly in industrial floors, seals and concrete
restoration products, composites (fiber composite materials),
potting compounds, paints and adhesives. An overview of resins and
hardeners, including their properties, and the use thereof in the
field of civil engineering may be found in H. Schuhmann, "Handbuch
Betonschutz durch Beschichtungen" [Handbook of Concrete Protection
using Coatings], Expert Verlag 1992, pp. 396-428. The use of resins
and hardeners in the field of composites is described in P. K.
Mallick, "Fiber-Reinforced Composites, Materials, Manufacturing,
and Design", CRC Press, pp. 60-76.
[0003] As well as epoxy resins and hardeners, a standard curable
composition typically also comprises reactive diluents and
non-reactive constituents, for example catalysts, additives,
plasticizers, extenders or modifiers. These constituents on the one
hand have a positive effect on the reactivity and levelling of the
composition, but on the other hand the environment can be polluted
by continuous evaporation of non-reactive constituents not
incorporated into covalent bonds after conclusion of the
hardening.
[0004] A long-established modifier is benzyl alcohol. Benzyl
alcohol is miscible both with the epoxy resin and with the amine
hardener and has a viscosity-reducing and hence levelling-promoting
effect. Furthermore, benzyl alcohol catalyzes the curing reaction
of aminic hardeners and epoxy resins. Moreover, benzyl alcohol
suppresses unwanted carbamate formation, which is an accompanying
side reaction of the amine with the carbon dioxide from the ambient
air.
[0005] For the utilization of benzyl alcohol in epoxy resin
coatings, marked restrictions are to be expected in the future.
These arise, inter alia, from various national and international
guidelines (EU Decopaint guideline) for limitation of VOC (volatile
organic compound) emissions from coating materials and for
reduction of the health risk to the processor and user by volatile
and semi-volatile compounds (VOCs and SVOCs) (see demands of the
Ausschuss fur die gesundheitliche Bewertung von Bauprodukten=AgBB
[German Committee for Health-related Evaluation of Building
Products]) or the certification of buildings according to the
Deutsche Gesellschaft fur Nachhaltiges Bauen e. V. (DGNB) [German
Sustainable Building Council] or Leadership in Energy &
Environmental Design (LEED).
[0006] This gives rise to a high demand for the development of
novel epoxy systems that are free of benzyl alcohol.
[0007] The prior art discloses some approaches to a solution in
respect of this objective.
[0008] The German review article "Ohne Benzylalkohol geht's auch"
[Doing without Benzyl Alcohol] from Farbe and Lacke, 2010, 3,
mentions some auxiliaries, for example specific polyamidoamine
hardeners, specific low-viscosity high-boiling resins or else
high-boiling glycol ethers, in order to formulate a curable
composition without benzyl alcohol. It is possible in principle to
use auxiliaries, but this is associated with a lot of complexity
and high costs.
[0009] EP 2706076 B1 discloses benzyl alcohol-free epoxy
resin-based compositions having a tailored furfurylamine-based
hardener. However, the complex process for preparation thereof
makes it more expensive than standard aminic hardeners. As well as
the economic aspect, it is certainly made more difficult for these
"special" amine hardeners to make the commercial breakthrough
because the amine hardener in established systems cannot simply be
exchanged.
[0010] Benzyl alcohol-based alkoxylates are known to those skilled
in the art. For instance, benzyl glycols are described in WO
2005026275 and U.S. Pat. No. 8,129,032 B2 as additive in aqueous
dispersions. Use as dispersant for color pigments (JP4787416 B2, US
20060001011) or as emulsifier in aqueous epoxy-based dispersions
(JP 60019774 B, JP 60011728 B and JP 51033940 B) is also known.
[0011] Benzyl alcohol-based propoxylates are described in WO
9937714 A1 in the context of solvent-containing and solvent-free
epoxy resin systems. Phenol-based and benzyl alcohol-based
propoxylates are described therein as plasticizer for epoxy resin
and amine hardener. If such alkoxylates are used as a substitute
for benzyl alcohol in curable compositions, the gel time is
extended, leaving the surface hardness of the hardened material
virtually unaffected after 5 d.
[0012] It is therefore desirable to provide a modifier for curable
epoxy resin-based compositions, wherein these curable compositions
have a reduction in the VOC (volatile organic content) and SVOC
(semi-volatile organic content) values compared to comparable
benzyl alcohol-containing curable epoxy resin-based compositions,
and at the same time do not show any significant deterioration in
the processing-relevant properties of the curable composition.
[0013] To solve the problem, a modifier of the type mentioned at
the outset is proposed, wherein the benzyl alcohol-based alkoxylate
is obtained by reacting benzyl alcohol with alkylene oxides and has
at least one ethoxy fragment.
[0014] A modifier is understood in the context of this invention to
mean the following: It is an important constituent in a curable
composition that has a positive effect on the reactivity and
levelling of the composition. In the broadest sense, the modifier
of the invention is to represent the same function as the benzyl
alcohol known from the prior art for this purpose. Benzyl alcohol
is miscible both with the epoxy resin and with the amine hardener
and has a viscosity-reducing and hence levelling-promoting effect.
Furthermore, benzyl alcohol catalyzes the curing reaction and the
conversion of aminic hardeners and epoxy resins. The unwanted
formation of carbamate, as a side reaction of the unconverted amine
with the carbon dioxide from the ambient air, is thus counteracted
by the use of benzyl alcohol.
[0015] It has now been found that the curable composition produced
with the modifier according to the invention has lower outgassing
characteristics than curable compositions comprising benzyl
alcohols.
[0016] The outgassing characteristics are inferred on the basis of
the volatile content up to a boiling point of 365.degree. C. Up to
this range, the volatile constituents (VOCs) and semi-volatile
constituents (SVOCs) are recorded as a cumulative parameter. The
lower the percentage, the lower the level of volatile substances
that are released into the environment. The volatile fractions were
determined by gas chromatography to DIN EN ISO 11890-2. 365.degree.
C. is the limit for the SVOC (semi-volatile organic content).
[0017] It has likewise been found that, surprisingly, the modifier
according to the invention, with regard to the processing-relevant
properties, for example dilution effect, viscosity reduction and
hardening reaction, does not have any significant deterioration
compared to the standard benzyl alcohols.
[0018] Compared to benzyl alcohol-based propoxylates, the modifier
according to the invention additionally shows an improvement in at
least one processing-relevant property for the same alkoxy fragment
chain length.
[0019] In the case of use of the curable compositions according to
the invention, curable composition comprising the modifier
according to the invention, it was especially possible to detect a
distinct improvement in the reduction in viscosity compared to the
use of the benzyl alcohol-based propoxylates. Likewise recorded
were quicker hardening, better flowability and a lower tendency to
carbamate formation in the curable compositions.
[0020] Where chemical (empirical) formulae are used in the present
invention, the specified indices may be not only absolute numbers
but also average values.
[0021] The indices relating to polymeric compounds are preferably
average values.
[0022] Unless stated otherwise, percentages are figures in percent
by weight.
[0023] If measured values are reported hereinbelow, these
measurements, unless stated otherwise, have been conducted under
standard conditions (25.degree. C. and 1013 mbar).
[0024] When average values are reported hereinbelow, the values in
question are weight averages, unless stated otherwise.
[0025] Preferably, the benzyl alcohol-based alkoxylates according
to the invention are benzyl alcohol-based ethoxylates.
[0026] Preferably, the benzyl alcohol-based alkoxylates according
to the invention are benzyl alcohol-based mixed alkoxylates of the
formula (I):
##STR00001##
where a=alkoxy fragment (a)=1 to 10, preferably 2 to 7, especially
preferably 3 to 6, b=alkoxy fragment (b)=0 to 10, preferably 1 to
7, especially preferably 1 to 5, c=alkoxy fragment (c)=0 to 10,
preferably 0 to 6, especially preferably 0 to 3, R1,
R2=independently hydrogen, an alkyl group having 2 to 20 carbon
atoms, an aryl or alkaryl group, preferably an ethyl, octyl, decyl,
phenyl, especially preferably ethyl or phenyl, with the proviso
that R1 is not H when R2 is methyl, and that the two R1 and R2
radicals must not both be H at the same time, R3=independently a
hydrogen radical, an acetyl, phosphoric ester or alkyl group which
has 1 to 20 carbon atoms and may also have further substitution,
preferably an acetyl, methyl or phosphoric ester group or a
hydrogen radical, more preferably a hydrogen radical.
[0027] Preferably, the modifier according to the invention is
prepared by reaction of benzyl alcohol with alkylene oxides.
[0028] Benzyl alcohol (CAS: 100-51-6) is an aromatic alcohol also
known by the chemical names of phenylmethanol and phenylcarbinol.
It is a natural raw material present to an extent of about 6% in
jasmine blossom oil, but also in clove oil or wallflower oil.
[0029] It is generally possible to use all alkylene oxides known to
those skilled in the art. Preference is given to using, for
example, ethylene oxide (EO), propylene oxide (PO),
1,2-epoxy-2-methylpropane (isobutylene oxide), epichlorohydrin,
2,3-epoxy-1-propanol, 1,2-epoxybutane (butylene oxide, also
abbreviated hereinafter as BO), 2,3-epoxybutane,
2,3-dimethyl-2,3-epoxybutane, 1,2-epoxypentane,
1,2-epoxy-3-methylpentane, 1,2-epoxyhexane, 1,2-epoxycyclohexane,
1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane,
1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, styrene
oxide (also abbreviated hereinafter as SO), 1,2-epoxycyclopentane,
1,2-epoxycyclohexane, vinylcyclohexene oxide,
(2,3-epoxypropyl)benzene, vinyloxirane, 3-phenoxy-1,2-epoxypropane,
2,3-epoxy methyl ether, 2,3-epoxy ethyl ether, 2,3-epoxy isopropyl
ether, 3,4-epoxybutyl stearate, 4,5-epoxypentyl acetate,
2,3-epoxypropane methacrylate, 2,3-epoxypropane acrylate, glycidyl
butyrate, methyl glycidate, ethyl 2,3-epoxybutanoate,
4-(trimethylsilyl)butane 1,2-epoxide, 4-(triethylsilyl)butane
1,2-epoxide, 3-(perfluoromethyl)-1,2-epoxypropane,
3-(perfluoroethyl)-1,2-epoxypropane,
3-(perfluorobutyl)-1,2-epoxypropane,
3-(perfluorohexyl)-1,2-epoxypropane, 4-(2,3-epoxypropyl)morpholine,
1-(oxiran-2-ylmethyl)pyrrolidin-2-one.
[0030] All the alkylene oxides mentioned can be used individually
or in any desired mixtures for alkoxylation of the benzyl
alcohol.
[0031] Particular preference is given to using ethylene oxide,
propylene oxide, butylene oxide and styrene oxide.
[0032] In order, for example, to introduce the alkoxy fragments (a)
and (b) shown in formula (I) into the modifier according to the
invention, it is possible with preference to use ethylene oxide
(EO) for the alkoxy fragment (a) and to use propylene oxide (PO),
also known by the 1,2-epoxypropane name, for the alkoxy fragment
(b).
[0033] In order, for example, to introduce the alkoxy fragments (c)
specified in formula (I) into the modifier according to the
invention, it is possible with preference to use butylene oxide
(BO) and/or styrene oxide (SO) for the alkoxy fragment (c).
[0034] In a very particularly preferred embodiment, ethylene oxide
and propylene oxide are used in a molar ratio of 1:10 to 10:0,
preferably of 3:1 to 1:0, more preferably 3:3, 3:1, 4:0 or 1:1.
[0035] The alkoxy fragments (a), (b) and (c) may preferably have a
statistical distribution and/or blockwise distribution.
[0036] The required distribution of the alkoxy fragments (a) and/or
(b) and/or (c) can be achieved via the particular process regime
known to those skilled in the art, more particularly via the
addition sequence or the simultaneous addition of the respective
alkylene oxides (individually or as a mixture) and via their molar
ratio to one another.
[0037] The alkoxylation of the benzyl alcohol can be effected under
base, acid, or transition metal catalysis. The alkoxylation is
preferably conducted in the presence of double metal cyanide (DMC)
catalysts or bases. Particular preference is given to conducting
the alkoxylation in the presence of bases.
[0038] The base-catalyzed alkoxylation of benzyl alcohol is
preferably conducted at least partly with alkali metal hydroxide or
alkoxide, preferably sodium methoxide, potassium methoxide or
potassium hydroxide, more preferably potassium methoxide or
potassium hydroxide. The amount of alkali metal hydroxides or
alkoxides used is preferably from 1 to 15 mol %, more preferably
from 1.5 to 10 mol %, especially preferably 2 to 7 mol %.
[0039] The alkoxylation is preferably conducted at a temperature
between 80.degree. C. and 200.degree. C., preferably from 90 to
170.degree. C. and more preferably from 100 to 125.degree. C. The
conversion is preferably effected at pressures in the range from
0.001 to 100 bar, more preferably in the range from 0.005 to 10 bar
and most preferably from 0.01 to 5 bar (each absolute pressures).
If necessary, the alkoxylation can also be conducted in the
presence of an inert gas (for example nitrogen).
[0040] The terminal hydroxyl groups of the benzyl alcohol
alkoxylates may preferably remain in free form or may be modified
partly or completely in order to optimize compatibility in the
later application matrix.
[0041] Accordingly, the benzyl alcohol-based alkoxylate preferably
has a terminal hydroxyl group.
[0042] Conceivable modifications are transesterifications,
esterifications or etherifications, as are further condensation or
addition reactions with isocyanates, for example, which can be
conducted by any desired prior art methods.
[0043] Preferably, the terminal hydroxyl groups are acetylated,
methylated or phosphorylated, more preferably phosphorylated.
[0044] Preferably, the degree of alkoxylation is 3 to 10, more
preferably 4 to 8.
[0045] The polydispersity (Mw/Mn) of benzyl alcohol alkoxylates of
the formula (I), determined by means of GPC, is preferably <2.5,
more preferably <2.0 and especially preferably from >1.05 to
<1.5.
[0046] The invention further provides for the use of benzyl
alcohol-based alkoxylates, wherein the benzyl alcohol-based
alkoxylate has at least one epoxy fragment as modifiers for curable
compositions comprising at least one epoxy resin, at least one
hardener, preferably an aminic hardener or an acidic hardener, and
optionally further auxiliary components.
[0047] Preference is given to using the inventive benzyl
alcohol-based alkoxylates of formula (I) as modifiers.
[0048] The inventive benzyl alcohol alkoxylates of the formula (I)
can be used for various applications.
[0049] The present invention likewise provides curable compositions
comprising
(1) at least one epoxy resin, (2) at least one hardener (2a) of
aminic nature or (2b) of acidic nature, (3) at least one modifier
of formula (I), (4) optionally further auxiliary components.
[0050] Epoxy resins used, component (1) of the curable
compositions, may in principle be any epoxy resins that can be
hardened with amines. Essentially, epoxy resins are prepolymers
containing two or more epoxy groups per molecule. The most commonly
used are bisphenol-based glycidyl ethers or novolaks, usually
having viscosities of greater than 10 Pa*s.
[0051] Examples include bisphenol A diglycidyl ether, bisphenol F
diglycidyl ether or cycloaliphatic types, for example
3,4-epoxycyclohexylepoxymethane or 3,4-epoxycyclohexylmethyl
3,4-epoxycyclohexanecarboxylate.
[0052] Preference is given to using bisphenol A-based epoxy resins
and bisphenol F-based epoxy resins in the composition according to
the invention.
[0053] Aminic hardeners used, component (2a) of the curable
compositions, are typically aliphatic, cycloaliphatic, araliphatic
or aromatic amines or polyamines. Preference is given to using
amine-containing hardeners having at least two or more primary
and/or secondary amino groups. Examples of aliphatic amines include
diaminoethane, diaminopropane, diaminobutane, neopentanediamine,
diaminohexane, and also bis(aminocyclohexyl)methane,
diaminocyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane,
tricyclododecanediamine, norbornanediamine, TCD-diamine,
N-aminoethylpiperazine, isophoronediamine, 1,3- and/or
1,4-bis(aminomethyl)cyclohexane, trimethylhexamethylenediamine,
N-aminoethylpiperazine, 1,4-bis(aminopropyl)piperazine.
[0054] Aromatic amines used may preferably be methylenedianiline,
xylylenediamine, m-phenylenebis(methylamine). Polyetheramines used
may advantageously be polyoxyalkyleneamines such as
diethylenetriamine, triethylenetetramine, tetraethylenetetramine,
etc., and also dipropylenetriamine, tripropylenetetramine,
polyaminoamides, and reaction products of amines with acrylonitrile
and Mannich bases.
[0055] Acidic hardeners used, component (2b) of the curable
composition, are typically acids and acid anhydrides. Preference is
given to using carboxylic anhydrides or polymeric carboxylic
anhydrides, or resins or polymers containing carboxylic anhydrides.
Examples include phthalic anhydride, tetrahydrophthalic anhydride,
hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride,
3,6-endomethylenetetrahydrophthalic anhydride,
hexachloroendomethylenetetrahydrophthalic anhydride,
methyl-3,6-endomethylenetetrahydrophthalic anhydride, trimellitic
anhydride, maleic anhydride, acrylic anhydride, methacrylic
anhydride, hydroxymethylacrylic anhydride, hydroxyethylacrylic
anhydride, hydroxypropylacrylic anhydride.
[0056] The modifier used, component (3) of the curable
compositions, may preferably be a compound of the formula (I).
[0057] Auxiliary components used, component (4) of the curable
compositions, may be any component that has a positive effect on
the properties of the composition according to the invention. It is
independently possible to add one or more auxiliary components.
[0058] Listed hereinafter are some auxiliary components that can be
used for the curable composition according to the invention. The
enumeration is non-conclusive.
[0059] Auxiliary components usable advantageously are, for example,
reactive diluents. The term "reactive diluent" is understood in the
context of this invention to mean a low-viscosity glycidyl ether of
relatively low molecular weight which is compatible with the other
composition constituents. It is possible with preference to use,
for example, butyl glycidyl ether, ethylhexyl glycidyl ether,
phenyl glycidyl ether, glycidyl ethers of Versatic acid, C12/C14
glycidyl ethers, C13/C15 glycidyl ethers, p-tert-butylphenyl
glycidyl ether, hexane 1,6-diglycidyl ether, butane 1,4-diglycidyl
ether, cyclohexanedimethyl diglycidyl ether, polypropylene
diglycidyl ether, polyethylene diglycidyl ether, neopentyl glycol
diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane
triglycidyl ether and cresyl glycidyl ether.
[0060] Auxiliary components usable advantageously are, for example,
solvents. Mention should be made, for example, of xylene, hyblene
(CAS No. 67774-74-7) or isopropanol. However, the use of solvents
in the composition according to the invention is less
preferable.
[0061] Auxiliary components usable advantageously are, for example,
catalysts such as organic acids or tertiary amines. Examples
include salicylic acid, tris(N,N-dimethylaminomethyl)phenol,
aminoethylpiperazine.
[0062] Auxiliary components usable advantageously are, for example,
fillers. Examples include sand, silicates, graphite, talc, silicon
dioxide.
[0063] Auxiliary components usable advantageously are, for example,
plasticizers, dyes, pigments, stabilizers, extender resins,
deaerators, wetting agents and dispersants, surface additives,
substrate wetting agents, ESD additives (ESD=electrostatic
discharge), etc.
[0064] In the curable compositions according to the invention, it
is also advantageously possible to use any desired mixtures of
different epoxy resins (1) and/or amine hardeners (2a).
[0065] In the curable compositions according to the invention, it
is also advantageously possible to use any desired mixtures of
different epoxy resins (1) and/or acidic hardeners (2b).
[0066] In a particular embodiment of the present invention, it may
also be advantageous to use prepolymers of epoxy resins and amine
hardeners alone, or in a blend with further epoxy resin and/or
amine hardener, in the compositions according to the invention.
[0067] In the use of the modifier (3) according to the invention,
the user is given every freedom. The modifier (3) according to the
invention can be added in the course of production of the curable
composition. It is also possible to make prefabricated mixtures of
the modifier (3) according to the invention with the epoxy resin
(1). In addition, it is also possible to premix the modifier (3)
according to the invention with the amine hardener (2a) or the
acidic hardener (2b).
[0068] Alternatively, rather than monomeric resins or hardeners, it
is also possible to mix any desired prepolymers prepared therefrom
with the modifier (3) according to the invention. It is possible to
add the auxiliary component (4) either to the epoxy resin (1) or to
the hardener (2a) or (2b), or else to the modifier (3) according to
the invention or else to any desired mixtures of the aforementioned
components. In a preferred embodiment, the modifier (3) according
to the invention is added to the epoxy resin (1) or to the
respective hardeners (2a) or (2b) or is added in the course of
production of the curable composition, more preferably to the
hardeners (2a) or (2b) or in the course of production of the
curable composition.
[0069] For a composition which is advantageous in application
terms, a particular molar ratio of the epoxy groups of the epoxy
resin (1) to the amino groups of the hardener (2a) may be required.
In a preferred embodiment of the composition according to the
invention, the molar ratio of the epoxy groups of all epoxy resins
(1) in the composition to the amino groups of all aminic hardeners
(2a) is preferably between 1:0.5 and 1:1.5, more preferably 1:0.7
and 1:1.3, especially preferably 1:0.9 and 1:1.1.
[0070] Mixing ratios used of the composition composed of epoxy
resin (1), aminic hardener (2a) or acidic hardener (2b), the
modifier (3) according to the invention and further auxiliary
components (4) are, based on the total weight of the epoxy resin
(1) and the aminic hardener (2a), in the preferred embodiment, a
mass ratio to the modifier (3) according to the invention of
preferably between 1:0 and 1:1, more preferably between 1:0 and
1:0.5, especially preferably between 1:0 and 1:0.2. The mixing
ratio based on the total weight of the epoxy resin (1) and the
aminic hardener (2a) to further auxiliary components (4) is
preferably between 1:0 and 1:15, more preferably 1:0 and 1:8,
especially preferably 1:0 and 1:1.
[0071] The compositions according to the invention are usable
especially advantageously in floor coatings, protective coatings,
composites, adhesives and sealants in industrial construction,
storage and logistics, construction of administrative buildings and
other buildings, water protection, food and drink industry,
cleanrooms, park buildings, corrosion protection, concrete
protection, sealing of built structures, hygiene coating, other
industrial coatings and wall paints. Also included are applications
in which the coatings have additional functionalities and
properties, for example protection from corrosion, dissipation of
electrical current, fire protection.
[0072] The subject-matter of the invention is described by way of
example hereinafter, without any intention that the invention be
restricted to these illustrative embodiments.
Test Methods:
[0073] Parameters or measurements are preferably determined using
the methods described hereinbelow. In particular, these methods are
used in the examples of the present intellectual property
right.
[0074] In the context of this invention, weight-average and
number-average molecular weights are determined for the benzyl
alcohol alkoxylates of the formula (I) prepared by gel permeation
chromatography (GPC) calibrated against a polypropylene glycol
standard. GPC was conducted using an Agilent 1100 instrument fitted
with an RI detector and an SDV 1000/10000 .ANG. column combination
consisting of an 0.8.times.5 cm pre-column and two 0.8.times.30 cm
main columns at a temperature of 30.degree. C. and a flow rate of 1
ml/min (mobile phase: THF). The sample concentration was 10 g/l and
the injection volume was 20 pl.
[0075] The polydispersity index (PDI) is the quotient of Mw divided
by Mn (PDI=Mw/Mn).
[0076] The volatile fractions were determined by gas chromatography
to DIN EN ISO 11890-2. Before the measurement, the alcoholic end
groups were converted to the corresponding trimethylsilyl ethers by
derivatization with N-methyl-N-trifluoroacetamide (MSTFA).
[0077] The analysis was effected by means of gas chromatography
equipped with on-column injection and FID detection. The
constituents were separated on an apolar separation column (DB-5
HT; length 30 m; diameter 0.25 mm; film thickness 0.1 .mu.m,
temperature program 65.degree. C. to 365.degree. C. at 10.degree.
C. per minute, followed by hold time of 15 minutes at 365.degree.
C.).
[0078] For quantification, the sum total of the peak areas of the
constituents classified as VOC/SVOC was determined in comparison to
the total peak area of all substances detected in the sample (area
% evaluation).
[0079] Wet chemistry analysis was performed according to
international standard methods: iodine number (IN; DGF C-V 11 a
(53); acid number (AN; DGF C-V 2); OH number (ASTM D 4274 C).
[0080] The content of primary OH chain termini of the polyethers
was determined by the evaluation of quantitative 13C NMR spectra.
For this purpose, the intensity of the signals at a shift of
.about.62 ppm (primary OH groups) was expressed as a ratio with the
signals at .about.67 ppm (secondary OH groups).
[0081] The NMR spectra were measured with a Bruker 400 MHz
spectrometer using a 5 mm QMP head. Quantitative NMR spectra were
measured in the presence of a suitable accelerating agent. The
sample to be analyzed was dissolved in a suitable deuterated
solvent (methanol) and transferred into 5 mm or, if appropriate, 10
mm NMR tubes.
EXAMPLE 1
Synthesis of Benzyl Alcohol-Based Propoxylates and Modifiers
According to the Invention
Examples M1-M14, CM1 and CM2
[0082] A 5 liter autoclave is initially charged with the
appropriate amount of benzyl alcohol together with 5 mol % of
potassium methoxide under nitrogen. The reactor was inertized by
injecting nitrogen to 3 bar and then decompressing to standard
pressure. This operation was repeated twice more. While stirring,
the contents of the reactor were heated to 100.degree. C. and
evacuated to about 100 mbar to remove the methanol from the
catalysis step. Then the temperature was increased to 120.degree.
C. and the alkylene oxide(s) was/were metered in so as to give the
distribution of the alkoxy fragments specified in Table 1.
[0083] The dosage rate of the alkylene oxide(s) was chosen such
that the pressure in the reactor did not rise above 2 bar. After
the dosage had ended, there was at first a wait period until the
pressure ceased to fall, which was regarded as a sign of virtually
quantitative conversion of the alkylene oxide(s). To complete the
alkylene oxide conversion, further reaction was conducted for one
hour. When the aim is a blockwise alkoxy structure, the
above-described procedure is repeated for every pure alkylene oxide
to be added on. When the aim is statistical addition of the
alkylene oxides, a homogeneous mixture of the respective alkylene
oxides is metered in. Finally (after addition of the last alkylene
oxide or alkylene oxide mixture with appropriate further reaction),
the reaction mixture was deodorized by applying a pressure (p<20
mbar), in order to remove traces of unconverted alkylene oxide.
Subsequently, the benzyl alcohol-based alkoxylate was neutralized
with dilute phosphoric acid and stabilized with 500 ppm of ANOX 20
AM. Subsequently, the water was removed by distillation under
reduced pressure and the precipitated salts were filtered off.
[0084] In all cases, colorless to yellowish benzyl alcohol-based
alkoxylates were obtained, the essential indices of which are
summarized in Table 1. The structure described in the tables which
follow is explained as follows: If the alkoxy fragments (for
example EO or PO) are separated by a "+", the structure is a
blockwise structure; if the alkoxy fragments are separated by a
"/", the structure is a statistical structure. For simplification
of the representation in the tables, the alkoxy fragments were
referred to by the alkylene oxides used, EO, PO, BO and SO.
Example 1a
[0085] Acetylation of the modifier M1 according to the invention
Under protective gas, a 4 liter three-neck flask equipped with
dropping funnel and reflux condenser was initially charged with
1979 g of the modifier 1 together with catalytic amounts of
concentrated hydrochloric acid, and heated. Then acetic anhydride
was added gradually. On completion of addition, the mixture was
stirred at 100.degree. C. for another 4 h. Then acid residues
present were distilled off, and a terminally acetylated modifier
M1Ac with an acid number of 0.1 and a hydroxyl number of 0 mg KOH/g
was obtained.
[0086] In an analogous manner, the modifier M5 was also acetylated.
This gave a terminally acetylated modifier M5Ac with an acid number
of 0.1 and a hydroxyl number of 0 mg KOH/g.
Example 1b
[0087] Methylation of the modifier M1 according to the invention
Under protective gas, a 4 liter three-neck flask equipped with a
distillation system was initially charged with 1620 g of the
modifier M1 according to the invention and heated to 50.degree. C.
At this temperature, 130 mol % of sodium methoxide are added
gradually. The methanol formed is distilled off. Subsequently, a
water-jet vacuum is applied, the temperature is increased to
120.degree. C. and methyl chloride is introduced into the solution
with the aid of a gas inlet tube for 1.5 h. After another vacuum
distillation step, methyl chloride is again introduced over a
period of 1 h. Then the mixture is distilled, neutralized and
filtered, and a terminally methylated modifier M1Me with an acid
number of 0.1 and a hydroxyl number of 1.0 mg KOH/g is
obtained.
[0088] In an analogous manner, the modifier M5 was also methylated.
This gave a terminally methylated modifier M5Me having an acid
number of 0.1 and a hydroxyl number of 2.4 mg KOH/g.
TABLE-US-00001 TABLE 1 Structure and physical data of the benzyl
alcohol-based alkoxylates Prim. Benzyl alcohol- AN OHN OH based [mg
termini alkoxylates Structure KOH/g] [%] M1 Benzyl alcohol + 3 EO
0.1 220 100 M2 Benzyl alcohol + 6 EO 0.1 147 100 M3 Benzyl alcohol
+ 3 EO/3 PO 0.2 128 14 M4 Benzyl alcohol + 3 PO + 3 EO 0.3 136 74
M5 Benzyl alcohol + 2 EO/2 PO 0.3 180 19 M6 Benzyl alcohol + 1 EO/5
PO 0.1 132 0 M7 Benzyl alcohol + 2 EO/4 PO 0.1 133 0 M8 Benzyl
alcohol + 1 EO/3 PO 0.1 173 2 M9 Benzyl alcohol + 1 PO + 3 EO 0.1
186 71 M10 Benzyl alcohol + 3 EO + 1 PO 0.1 183 32 M11 Benzyl
alcohol + 1 EO/3 PO/2 0.2 118 0 BO M12 Benzyl alcohol + 1 EO/3 PO/2
0.3 105 0 SO M13 Benzyl alcohol + 2 EO/1 PO 0.2 267 31 M14 Benzyl
alcohol + 1 EO/2 PO 0.3 270 5 M1Ac Benzyl alcohol + 3 EO, 0.1 0 0
acetylated M5Ac Benzyl alcohol + 2 EO/2 PO, 0.1 0 0 acetylated M1Me
Benzyl alcohol + 3 EO, 0.1 1 100 methylated M5Me Benzyl alcohol + 2
EO/2 PO, 0.1 2.4 0 methylated CM1 Benzyl alcohol + 3 PO 0.2 194 0
(comparative example) CM2 Benzyl alcohol + 6 PO 0.1 117 0
(comparative example)
[0089] M1 to M14 are modifiers according to the invention. CM1 and
CM2 are comparative examples.
EXAMPLE 2
Outgassing Characteristics
[0090] The outgassing characteristics of the inventive modifier
M1-12 or of the benzyl alcohol or of the comparative examples is
inferred on the basis of the volatile content (VOCs and
SVOCs=volatile and moderately volatile organic compounds) in
accordance with the definition of DIN EN 11890-2. The volatile
fractions are determined by gas chromatography according to DIN EN
ISO 11890-2. Before the measurement, the alcoholic end groups were
converted to the corresponding trimethylsilyl ethers by
derivatization with N-methyl-N-trifluoroacetamide (MSTFA). The
analysis was effected by means of gas chromatography equipped with
on-column injection and FID detection. The constituents were
separated on an apolar separation column (DB-5 HT; length 30 m;
diameter 0.25 mm; film thickness 0.1 .mu.m, temperature program
65.degree. C. to 365.degree. C. at 10.degree. C. per minute,
followed by hold time of 15 minutes at 365.degree. C.). For
quantification, the sum total of the peak areas of the constituents
classified as VOC/SVOC was determined in comparison to the total
peak area of all substances detected in the sample (area %
evaluation). The lower the percentage, the lower the level of
volatile substances that are released into the indoor
environment.
TABLE-US-00002 TABLE 2 Volatile organic content of modifiers
according to the invention compared to benzyl alcohol Volatile
content up to a boiling point of 365.degree. C. Structure % Benzyl
Benzyl alcohol 100 alcohol M1 Benzyl alcohol + 3 EO 58.6 M2 Benzyl
alcohol + 6 EO 11.7 M3 Benzyl alcohol + 3 EO/3 PO 18.8 M5 Benzyl
alcohol + 2 EO/2 PO 67.2 M6 Benzyl alcohol + 1 EO/5 PO 17.2 M7
Benzyl alcohol + 2 EO/4 PO 15.4 M8 Benzyl alcohol + 1 EO/3 PO 65.9
M9 Benzyl alcohol + 1 PO + 3 EO 60.0 M10 Benzyl alcohol + 3 EO + 1
PO 63.7 M11 Benzyl alcohol + 1 EO/3 PO/2 18.4 BO M12 Benzyl alcohol
+ 1 EO/3 PO/2 13.1 SO M13 Benzyl alcohol + 2 EO/1 PO 61.2 M14
Benzyl alcohol + 1 EO/2 PO 61.0 M1Ac Benzyl alcohol + 3 EO, 52.3
acetylated M5Ac Benzyl alcohol + 2 EO/2 PO, 61.6 acetylated M1Me
Benzyl alcohol + 3 EO, 54.7 methylated M5Me Benzyl alcohol + 2 EO/2
PO, 63.5 methylated CM1 Benzyl alcohol + 3 PO 65.4 CM2 Benzyl
alcohol + 6 PO 12.2
[0091] All modifiers according to the invention are superior to
benzyl alcohol in terms of outgassing characteristics. It is
additionally found that the inventive M1 compared to CM1 (equal
chain length) and the inventive M2 compared to CM2 (equal chain
length) release a lower level of volatile organic compounds.
EXAMPLE 3
Measurement of Viscosity of the Modifier According to the Invention
in Epoxy Resin Binders
[0092] The modifier according to the invention is used in epoxy
resin binders without catalyst and in epoxy resin binders with
catalyst, in order to examine the effect thereof on viscosity.
TABLE-US-00003 Formulation I Proportion Epikote 828, binder from
Hexion 20 g M1, M1Ac, M1Me, M2-M5, M5Ac, 2 g M5Me, M6-M10, M13,
M14, CM1-2, benzyl alcohol
TABLE-US-00004 Formulation II Proportion Epikote 828, binder from
Hexion .sup. 20 g M1-M3, M5-M8, M13, M14, CM1-2, 2 g benzyl alcohol
Salicylic acid (catalyst) 0.55 g
[0093] The binder was initially charged in PE cups, the inventive
modifier or benzyl alcohol or comparative examples (CM) and
optionally catalyst was metered in, and the formulations were each
incorporated in a Hauschild Speedmixer at 1000 rpm for 1 min. The
viscosities of the formulations were measured with an Anton Paar
MCR 102 rheometer. Measurement parameters: cone/plate CP 25/2,
23.degree. C., multiple measurement points in the range of 1-1000
1/s.
TABLE-US-00005 TABLE 3.1 Influence of the inventive modifier on the
viscosity of formulation I Formula- Viscos- Viscos- Viscos- tion I
ity at ity at ity at com- 10 1/s 100 1/s 1000 1/s prising Structure
mPas mPas mPas Benzyl Benzyl alcohol 1710 1720 1670 alcohol M1
Benzyl alcohol + 3 EO 3970 3990 3690 M1Ac Benzyl alcohol + 3 EO,
3940 3980 3690 acetylated M1Me Benzyl alcohol + 3 EO, 3210 3000
2890 methylated M2 Benzyl alcohol + 6 EO 4970 5040 4570 M3 Benzyl
alcohol + 3 EO/3 PO 5650 5710 5100 M4 Benzyl alcohol + 3 PO + 3
5877 5821 5067 EO M5 Benzyl alcohol + 2 EO/2 PO 4470 4510 4130 M5Ac
Benzyl alcohol + 2 EO/2 4330 4270 3950 PO, acetylated M5Me Benzyl
alcohol +2 EO/2 3910 3580 3240 PO, methylated M6 Benzyl alcohol + 1
EO/5 PO 5620 5630 5010 M7 Benzyl alcohol + 2 EO/4 PO 4870 4890 4440
M8 Benzyl alcohol + 1 EO/3 PO 3610 3660 3430 M9 Benzyl alcohol + 1
PO + 3 6104 5932 5186 EO M10 Benzyl alcohol + 3 EO + 1 5726 5662
5034 PO M13 Benzyl alcohol + 2 EO/1 PO 3226 3270 3142 M14 Benzyl
alcohol + 1 EO/2 PO 3163 3191 3073 CM1 Benzyl alcohol + 3 PO 4370
4410 4040 CM2 Benzyl alcohol + 6 PO 6280 6300 5520
TABLE-US-00006 TABLE 3.2 Influence of the inventive modifier on the
viscosity of formulation II Formula- Viscos- Viscos- Viscos- tion
II ity at ity at ity at com- 10 1/s 100 1/s 1000 1/s prising
Structure mPas mPas mPas Benzyl Benzyl alcohol 2650 2640 2510
alcohol M1 Benzyl alcohol + 3 EO 5310 5310 4750 M2 Benzyl alcohol +
6 EO 6670 6710 5820 M3 Benzyl alcohol + 3 EO/3 7080 7110 6100 PO M5
Benzyl alcohol + 2 EO/2 6140 6180 5440 PO M6 Benzyl alcohol + 1
EO/5 7680 7670 6480 PO M7 Benzyl alcohol + 2 EO/4 6850 6880 5950 PO
M8 Benzyl alcohol + 1 EO/3 6870 6900 6000 PO M13 Benzyl alcohol + 2
EO/1 5180 5150 4520 PO M14 Benzyl alcohol + 1 EO/2 5320 5360 4680
PO CM1 Benzyl alcohol + 3 PO 6260 6320 5530 CM2 Benzyl alcohol + 6
PO 7960 7950 6650
Summary of Tables 3.1 and 3.2:
[0094] If the inventive modifier M1 and CM1, having the same chain
length, are compared with one another, and analogously the
inventive M2, M3, M6 and M7 with CM2 (equal chain length), the
modifiers having ethoxy fragments are always superior to the
comparative examples with pure PO in terms of the
viscosity-lowering effect.
[0095] In addition, the viscosity-lowering effect can be enhanced
by an end modification. It is apparent from Table 3.1 that the
viscosity-lowering effect of the formulation I comprising M1Me or
M5Me according to the invention is somewhat better than that of the
formulation I comprising the unmodified M1 or M5 according to the
invention.
EXAMPLE 4
Reaction Rate of Epoxide Hardening
Assessment of Reactivity of Curable Compositions According to the
Invention on the Basis of Doubling of the Viscosity
[0096] The doubling of the initial viscosity is a measure of the
reaction rate of the epoxy hardening reaction.
Composition I
TABLE-US-00007 [0097] Proportion Epikote 828, binder from Hexion
.sup. 20 g M1, M2, M3, CM1-2, benzyl alcohol 2 g Vestamin IPD,
hardener from Evonik 4.54 g Resource Efficiency GmbH
[0098] The binder was initially charged in PE cups, the inventive
modifier or benzyl alcohol or comparative examples was metered in,
and the mixtures were each incorporated in a Hauschild Speedmixer
at 1000 rpm for 1 min. The hardener was weighed in and the curable
compositions were stirred in the Speedmixer at 2000 rpm for 1 min.
The viscosities of the curable compositions were measured with an
Anton Paar MCR 102 rheometer. Measurement parameters: cone/plate
25/2, 23.degree. C., constant shear rate of 100 1/s, measurement
lasts until doubling of the start value.
TABLE-US-00008 TABLE 4 Influence of the inventive modifier in a
curable composition I on reactivity on the basis of doubling of the
viscosity Compo- Starting Final Prim. sition I vis- vis- OH com-
cosity cosity Time termini prising Structure mPas mPas s % Benzyl
Benzyl alcohol 1490 2980 1790 100 alcohol M1 Benzyl alcohol + 3 EO
1720 3440 3100 100 M2 Benzyl alcohol + 6 EO 1710 3420 3350 100 M3
Benzyl alcohol + 3 EO/3 1760 3520 3580 14 PO CM1 Benzyl alcohol + 3
PO 1720 3440 3900 0 CM2 Benzyl alcohol + 6 PO 1870 3520 3680 0
[0099] If the inventive modifier M1 and CM1 are compared with one
another, both having the same chain length, and the inventive M2
and M3 are compared with CM2, curable compositions react more
quickly with the inventive modifiers having ethoxy fragments than
with those having pure propoxy fragments.
EXAMPLE 5
Curing
Influence of the Inventive Modifier in a Curable Composition on
Hardening
[0100] For the testing of Shore D hardness, the formulation of
curable composition I was used.
[0101] The binder was initially charged in PE cups, the inventive
modifier was metered in, and the mixtures were each incorporated in
a Hauschild Speedmixer at 1000 rpm for 1 min. The hardener was
weighed in and the curable compositions were stirred in the
Speedmixer at 2000 rpm for 1 min. This was used to cast a slab of
layer thickness about 5 mm. The Shore D hardnesses were measured
after various intervals.
TABLE-US-00009 TABLE 5 Evolution of Shore D hardness of curable
compositions according to the invention Shore D Shore D hardness
hardness after 2 after 7 Composition days days I comprising
Structure Shore Shore Benzyl Benzyl alcohol 86.3 88.6 alcohol M1
Benzyl alcohol + 3 EO 86.2 88.7 M1Ac Benzyl alcohol + 3 EO, 83.9
88.9 acetylated M1Me Benzyl alcohol + 3 EO, 83.8 87.5 methylated M2
Benzyl alcohol + 6 EO 84.4 88.4 M3 Benzyl alcohol + 3 EO/3 PO 84.5
85.9 M5 Benzyl alcohol + 2 EO/2 PO 85.1 88.1 M5Ac Benzyl alcohol +
2 EO/2 PO, 83.2 88.0 acetylated M5Me Benzyl alcohol + 2 EO/2 PO,
83.6 87.9 methylated M6 Benzyl alcohol + 1 EO/5 PO 85.2 87.6 M7
Benzyl alcohol + 2 EO/4 PO 85.0 87.5 M8 Benzyl alcohol + 1 EO/3 PO
82.3 87.1 M9 Benzyl alcohol + 1 PO + 3 EO 83.7 87.0 M10 Benzyl
alcohol + 3 EO + 1 PO 85.9 87.0 M11 Benzyl alcohol + 1 EO/3 PO/2
83.3 86.8 BO M12 Benzyl alcohol + 1 EO/3 PO/2 82.6 85.9 SO M13
Benzyl alcohol + 2 EO/1 PO 86.5 89.6 M14 Benzyl alcohol + 1 EO/2 PO
87.2 89.6 CM1 Benzyl alcohol + 3 PO 78.6 88.7 CM2 Benzyl alcohol +
6 PO 81.6 87.4
[0102] Curable compositions comprising the modifiers according to
the invention show comparable evolution of heat after 2 days to the
composition comprising benzyl alcohol. CM1 and CM2 having propoxy
fragments are distinctly inferior in terms of initial hardness.
EXAMPLE 6
Moisture Sensitivity
[0103] A measure used for the moisture sensitivity of an epoxy
coating is the tendency to carbamate formation. For this purpose, a
small piece of sponge is soaked with water, the sponge is placed
onto the coating and a bull's-eye (glass hemisphere) is mounted
above it. The surface is assessed at intervals. The carbamate
formed on the surface has a whitish appearance. Assessment is made
on a scale from 1 (very significant carbamate formation) to 5 (no
carbamate formation).
[0104] Curable composition II for production of the epoxy
coating
TABLE-US-00010 Proportion Epikote 828, binder from Hexion .sup. 20
g M1, 2, 3, 5-14, CM1-2, benzyl alcohol 1 g Vestamin IPD, hardener
from Evonik 4.54 g Resource Efficiency GmbH
[0105] The binder was initially charged in PE cups, the inventive
modifier or benzyl alcohol or comparative examples was metered in,
and the mixtures were each incorporated in a Hauschild Speedmixer
at 1000 rpm for 1 min. The hardener was weighed in and the curable
compositions were stirred in the Speedmixer at 2000 rpm for 1 min.
This was used to cast a slab of layer thickness about 5 mm.
Carbamate formation was assessed after 1, 2 and 7 days.
TABLE-US-00011 TABLE 6 Carbamate formation on a coating comprising
inventive modifiers compared to benzyl alcohol Composition II after
after after comprising Structure 1 d 2 d 7 d Benzyl Benzyl alcohol
5 5 5 alcohol M1 Benzyl alcohol + 3 EO 5 5 5 M1Ac Benzyl alcohol +
3 EO, 3 3 3 acetylated M1Me Benzyl alcohol + 3 EO, 2 2 3 methylated
M2 Benzyl alcohol + 6 EO 1 4 5 M3 Benzyl alcohol + 3 EO/3 PO 2 4 4
M5 Benzyl alcohol + 2 EO/2 PO 1 2 5 M5Ac Benzyl alcohol + 2 EO/2
PO, 2 3 3 acetylated M5Me Benzyl alcohol + 2 EO/2 PO, 2 2 3
acetylated M6 Benzyl alcohol + 1 EO/5 PO 3 4 5 M7 Benzyl alcohol +
2 EO/4 PO 3 3 5 M8 Benzyl alcohol + 1 EO/3 PO 2 4 4 M9 Benzyl
alcohol + 1 PO + 3 EO 5 5 5 M10 Benzyl alcohol + 3 EO + 1 PO 5 5 5
M11 Benzyl alcohol + 1 EO/3 PO/2 3 3 3 BO M12 Benzyl alcohol + 1
EO/3 PO/2 3 2 3 SO M13 Benzyl alcohol + 2 EO/1 PO 5 5 5 M14 Benzyl
alcohol + 1 EO/2 PO 3 4 4 CM1 Benzyl alcohol + 3 PO 2 2 3 CM2
Benzyl alcohol + 6 PO 1 2 3
[0106] Coatings comprising inventive modifiers with ethoxy
fragments show comparable moisture sensitivity to the coating
comprising benzyl alcohol. Comparative examples comprising propoxy
fragments only are distinctly inferior.
* * * * *